Fungicidal compositions



United States Patent M 3,224,933 FUNGICIDAL COMPOSITIONS William E.Burt, Royal Oak, Mich., assignor to Ethyl Corporation, New York, N.Y., acorporation of Virginia No Drawing. Filed Dec. 22, 1961, Ser. No.161,383 4 Claims. (Cl; 167-30) This invention relates to fungicidalcompositions, and more particularly, to fungicidally potent Group VIBmetal compounds and their use in combating fungi.

An object of this invention is to provide new fungicidal compositions.Still another object is to provide a new means for combating fungi. Afurther object is to provide new fungicidal compositions comprisingconditioning agents and certain organometallic compounds as describedherein.

The above and other objects are accomplished by the present inventionwhich resides in providing fungicidal compositions comprising aconditioning agent and as a principal active ingredient, a compoundhaving the where M is a metal of Group VIB of the Periodic Tableaccording to Mendeleev; R is selected from the class consisting ofhydrogen and univalent hydrocarbon radicals having one to about eightcarbon atoms selected from the class consisting of alkyl, cycloalkyl andaralkyl radicals, a is an integer ranging in value from zero to four,such that when a is greater than one, the sum of carbon atoms appendedto the ring ranges from two to about 8 carbon atoms; X is selected fromthe class consisting of halogen, CN and Group IA, IB, HA, and IIBmetals, and n is an integer such that when X is monovalent, n=l, andwhen X is divalent, n=2.

The halocompounds illustrated in the formula above (when X is a halogen)can be prepared according to the procedure given in Piper et al., J.Inorg. and Nucl. Chem., 3, 104 (1956). That paper also describes amethod for preparing the alkali metal cyclomatic Group VIB metaltricarbonyls called for above. The alkali metal compounds can be used toprepare the salts of the other metals in the above generic formula,according to the procedure reported by Fischer et al., Z. Naturforsch.105, 140 (1955).

The compounds described and illustrated above, wherein M is chromium ormolybdenum, are preferred. The most preferred metal is chromium, sincecompounds of this metal can be prepared more economically than compoundsof the other metals and, chromium compounds of this class are morestable.

More preferred compounds are illustrated by the formula given above inwhich X is a metal. The more preferred metals are those of Group IIB ofthe Periodic Table. The most preferred metal is mercury. Representativesof this class are the mercuric salts of cyclopentadienyl chromiumtricarbonyl and methylcyclopentadienyl molybdenum tricarbonyl, the zincsalt of tertiary butyl cyclopentadienyl chromium tricarbonyl, thecadmium salt of cyclopentadienyl chromium tricarbonyl and the like. Themost preferred compounds are the mercuric salt of cyclopentadienylchromium tricarbonyl and the mercuric salt of methylcyclopentadienylmolybdenum tricarbonyl.

X can also be a halogen or a cyanide radical. preferred compounds arethe halogen derivatives. The most preferred halogen is iodine. The iodocompounds are more stable than the other analogous halogen compounds. Anillustrative but not limiting list of compounds represented by theformula above, wherein X is The 3,224,933 Patented Dec. 21, 1965 ahalogen, is cyclopentadienyl chromium tricarbonyl iodide,cyclopentadienyl molybdenum tricarbonyl bromide, methylcyclopentadienylmolybdenum tricarbonyl iodide, cyclopentadienyl molybdenum tricarbonyliodide and the like. The most preferred compound is cyclopentadienylmolybdenum tricarbonyl iodide.

Thus, the preferred compounds are those illustrated by the above formulawherein M is either chromium or molybdenum and X is either iodine ormercury. The cyclopentadienyl radical which appears in the compounds ofthis class is preferably unsubstituted or monosubstituted rather thanmultisubstituted. The preferred compounds are those having anunsubstituted cyclopentadienyl ring or only one radical having one tofour carbon atoms. These compounds are preferred since these cyclopentadienyl radicals are more commercially readily available. Representativecyclopentadienyl radicals present in the fungicidally active ingredientsof this invention are the cyclopentadienyl radical and theethylcyclopentadienyl radical, cyclohexyl cyclopentadienyl,isopropylcyclopenta dienyl radicals and the like. ethylcyclopentadienylradicals are preferred.

Such compounds as described above are useful in combating fungi whenthey are applied to the locus of the fungi. Such treatment, therefore,constitutes one aspect of the invention. It has been found that theabove materials are useful in controlling and eliminating fungi whichinfest vegetables, animals and man. A facet of this invention is a novelmethod of combating and controlling;

For maximum effectiveness, the active ingredient of the presentinvention is admixed in fungicidally effective amount with aconditioning agent of the type commonly referred to as a pest controlledadjuvant or modifier. Such adjuvants have been referred to by names suchas conditioning agent, dispersing agent, surface active agent, andsurface active dispersing agent. Their purpose is to extend the activeingredient to assure its efiicacious penetration of, or application to,the locus being treated and to adapt the active ingredients for readyand efiicient application by using conventional equipment.

An advantage of using these conditioning agents is that the fugicidallyactive compounds may he too effective or two potent when used alone tobe of practical utility. Another advantage derived from the use of theseadjucants is to permit field application by methods readily employed andstill obtain effectively complete coverage of the material beingprotected.

Formulations of the fungicidally active ingredient with a suitableconditioning agent comprise both liquid and solid types as Well as theaerosol type of formulation. The liquid type of formulation can havewater, an organic solvent, or an oil-Water emulsion and the like as theconditioning agent.

It is also intended that the term conditioning agent include solidcarriers such as talc, ataclay, kieselguhr, chalk, diatomaceous earth,and the like, and various min eral powders, such as calcium carbonate,which act as a dispersant, as a carrier, and in some instances, performthe function of a surface active agent.

The conditioning agent may also be an industrial commodity such aspaint, raw polymer, finished plastic and the like. Such industrialmaterials act as a diluent, dispersant, wetting agent, and extender forthe active ingredient, thus, enhancing its fungical action.

The cyclopentadienyl and- The formulations of this invention, therefore,comprise the above defined fungicidally active ingredient in a suitablematerial as a dispersant or conditioning agent. It is not intended thatthis invention be limited to any specific proportions of activeingredient and conditioning agent. The important feature of theinvention is to provide a formulation of such concentration that isappropriate for the desired application. The conditioning agent will bepresent to provide the proper type of contact with the material beingprotected.

Nor is it intended that the invention be limited to the use of afungicidally active ingredient in the presence of only a compound orproduct or material known as a conditioning agent. It has been foundthat other additives are useful in the preparation of the fungicidalpreparations. Other materials found useful are classified as spreadingagents and adhesives. Spreading agents tend to increase the area coveredby a spray liquid. Many chemicals act as both wetting and spreadingagents. Dried blood (blood albumin), sulfite lye, both in the liquid anddehydrated forms, and petroleum emulsion belong to this group. Adhesivesincrease the adherence of the active agent to the treated surface toaugment resitance to wear and mechanical action. Bentonite and otherclays, gelatin and glue, are examples of adhesives.

As mentioned previously, the fungicidal preparations are in the form ofeither liquid or dry or aerosol formulations. Liquid compositions,either solutions or dispersions, frequently also contain a surfaceactive dispersing agent in amounts sufficient to render the compositionreadily useful in aqueous spray application. The surface activedispersing agents referred to herein are sometimes known as wetting,dispersing or penetrating agents. They are agents which cause theformulations to be easily dispersed in Water. They can be of theanionic, cationic, or nonionic type and include salts of long chainfatty acids, sulfonated oils, bot-h vegetable and animal, petroleumoils, sulfates of long chain alcohols, phosphates of long chainalcohols, various polyethylene oxides, condensation products of ethyleneoxide with alcohol and phenols, quaternary ammonium salts, and the like.The surface active agent will usually be present to the extent of 0.1 to5 percent of the formulation. Typical of the liquid formulations is thewater solution or dispersion of the active ingredients. Ex ample Ibelow, is an example for the preparation of an aqueous suspension of atypical active ingredient described in this invention.

The active ingredients can also be dispersed or suspended in variousorganic solvents such as alcohols, ketones, hydrocarbons, and petroleumfractions such as kerosene, dimethylformamide, and the like. In thesecases a surface active dispersing agent is usually present to provideready dispersability with water.

The solubility of the active ingredients of this invention in organicsolvents, furthermore, is such that they can be applied advantageouslyin the form of a solution in this type of solvent. In certain uses, thistype of vehicle is preferred, for example, in treating cloth, leather,or other fibrous articles. In these applications, it is preferred toapply the pesticides dissolved in a volatile solvent. After application,the volatile solvent evaporates leaving the fungicide impregnatedthroughout the surface of the article and in the dispersed form whichhas been found to be most advantageous. Likewise, in applying thefungicides to smooth surfaces, as for example in treating wood, asolution may be the most practical vehicle for applying the protectivefilm. Brushing, spraying, or dipping may be the application method ofchoice. The choice of an appropriate solvent is determined largely bythe solubility of the active ingredients which it is desired to employ,by the volatility required in the solvent, by the spreading or flowcharacteristics thereof, and by the nature of the material beingtreated. Typical formulation of this type is described in Example IIbelow.

Another typical formulation of the fungicidal ingredients is an oil inwater emulsion (see Example III). Generally these are prepared bydissolving the fungicidally active ingredient in an organic solvent,usually a petroleum fraction like kerosene, and then dispersing thissolution with vigorous agitation in a large volume of water containing aminor amount of a surface active agent.

In addition to the adjuvants and other ingredients described above, ithas been found that one can incorporate an adherent or sticking agentsuch as vegetable oils, naturally occurring gums, and other adhesivesinthe active ingredient formulations. Likewise, humectants can beemployed in the formulations. Furthermore, the formulations can beemployed in admixture with other pesticidal materials or other biocidessuch as insecticides, larvacides, bactericides, germicides, miticides orwith other materials which it is desired to apply along with thefungicides. In like manner, two or more of the active ingredients may beformulated together in a single composition, thus achieving control of abroader spectrum of fungi.

Fungicides can be applied in dry media as well as in liquid suspensionsor solutions. In fact, early practice in the art used dust formulationsalmost exclusively. It was only the advent of the introduction of spraymachinery that caused dust formulations to be considered with disfavor.However, it was soon realized that spraying was often not as convenientas dusting, particularly when large, comparatively inaccessiblecultivated fields are to be treated or when the area of interestnecessarily requires that it be treated with a dry agent. Dustformulations of my active compounds have a ready place in the art andindeed the use of these dry formulations should grow with time, sincethey are utilizable when treating large areas for fungicidal infestationby airplane dusting. Dusting is also extensively employed in treatingman and animals for fungicidal infestations.

A measure of the utility of the dust formulation is the impressiveamount of research which has been performed in this area. The particlesshape, the size, density and hardness, and the nature of the dry diluenthave been shown to be factors which are important as well as theabsorption and absorption characteristics thereof. Therefore, anotherdesired and efficacious formulation of the fungicidally activeingredient is a dust formulation which is prepared generally by millingthe active ingredient in ball mill within the presence of a drymaterial, for example, fullers earth. After milling, the mixture isscreened and the fraction passing through a very fine sieve iscollected. Thereafter, a further dilution is made by repeating the aboveprocedure with an additional very large amount of a compound such asfullers earth. Example IV exemplifies a dust formulation. A preferredformulation of the compounds comprises a wettable powder. In preparingwettable powders, several formulation procedures are possible (seeExample V for one type of procedure). It is one intention of thisinvention to provide compositions comprising the active ingredientdefined herein in combination with a minor amount of surface activeagent. Such surface active agents can be chosen for example from thosepreviously mentioned in connection with aqueous dispersion. Still othersurface active agents can be employed, the above merely showing arepresentative list of the more common material. Such formulations canbe readily admixed with a solid carrier. Formulations thus formed thencomprise the active ingredient of this invention, an inert carrier, anda surface active agent. Among the inert carriers which can be employedin preparing wettable powders are soya bean flour, tobacco flour, walnutshell flour, gypsum. mica, talc, apatite, pumice and the like. Inpreparing concentrated wettable powders it is preferred to employbetween 0.01 and 5 percent of the surface active agent,

based upon the amount of active ingredient, and up to 51 85 percent ofthe inert carrier based upon the total amount of the formulation. Suchconcentrated formulations provide the advantage of permitting economicalstorage and transportation of the fungicide and permit further dilutionby simple admixture, with water at the time of application.

The'compounds described above are also active in colloidal formulations.A colloidal formulation is prepared by passing a mixture of the activeingredient, a hydrocarbon solvent and a large amount of water through acolloid mill until homogenation of the oil and water is achieved.Example VI gives an example of the preparation of a colloidalformulation.

The compounds also find effective use when formulated in aerosolformulations, i.e., when mixed with a liquid of low boiling point thatchanges to a gas when released from a confined space. Examples ofdiluent used in these formulations are fluorinated hydrocarbons such astetrafiuoromethane, and hexafluoroethane. Mixed halogenated compoundscontaining fluorine and chlorine such as difluorodichloromethane andpentafluorochloroethane and the like can also be used as the liquidhaving the necessary low boiling point. Other materials such as carbondioxide, sulfur dioxide, hydrogen sulfide and ammonia can be used, andof these, carbon dioxide generally is preferred. One method of preparingsuch aerosol formulations comprises introducing my new compounds into apressure cylinder and later introducing the liquifying diluent underpressure followed by mixing the cylinder to obtain uniform solution. Ifdesired, smaller containers can then be filled from the cylinder inwhich the formulation is prepared. In many cases it is desirable to adda second solvent to the low boiling material of the type described aboveso as to more readily dissolve my compounds. Examples of suchco-solvents are benzene, acetone, carbon tetrachloride and the like.Example VII is an example of the preparation of an aerosol typeformulation of my active ingredient.

My compounds are also effective when formulated in an ointment fortopical application to the epidermis of animals and man. A typicalointment formulation is given in Example VIII below.

It is not intended that the finished formulations of my fungicidallyactive compounds be limited to any particular concentration range. Theconcentration range desired in my invention is that range necessary toaccomplish the desired end. A preferred range for agriculturalapplication is between 0.1 and 2,000 parts per million. Formulationscontaining as high as 30 percent active ingredient are used in treatinganimals and man. Typical formulations of this invention are described inthe following examples in which all parts are by weight.

The compounds in the following examples will have the designations givenbelow.

EXAMPLE I (WATER SUSPENSION) A formulation of Compound I is prepared byadding, with vigorous agitation, parts of this material to 1,000 partsof water containing 1 part of Tween-80. This conmolybdenum tricarbonyl6. centrated dispersion is further diluted 1,000 times by the additionof water to obtain a formulation of suitable concentration forapplication. Thus, the resulting dispersion contains 10 parts permillion of my fungicide in the water dispersion.

EXAMPLE II (ORGANIC SOLUTION) A solution consisting of 5 parts ofCompound II in 250 parts of cyclohexanone is prepared by stirring thetwo contituents for a period of two minutes at a temperature of about 25C. This concentrated solution suitable for storage or transportation isfurther diluted with 99,750 parts of kerosene to form a final dilutionof 50 p.p.m. suitable. for application.

EXAMPLE III (OIL IN WATER EMULSION),

An oil and water emulsion is prepared by dissolving 10 parts of CompoundIII in 1,000 parts of kerosene. This solution is dispersed with vigorousagitation in 99,000 parts of water containing one part of Triton X- toprovide a dispersion, containing 100 p.p.m. of active ingredient.

EXAMPLE IV (DUST FORMULATION) EXAMPLE V (WETTABLE POWDER) A mixture of100 parts of Compound V, 1,000 parts of att-aclay and 0.01 part ofNacconol is intimately mixed in an L-shaped blender. The 10 percentwettable powder thus prepared produces a satisfactory water suspensionwhen 11 parts are stirred into 10,000 parts of water, producing asuspension containing 100 p.p.m. active ingredient.

EXAMPLE VI (COLLOIDAL FORMULATION) A colloidal formulation is preparedby passing a mixture of 10 parts of Compound VI, 100 parts of kerosene,1000 parts of water and 1 part of mannitan monooleate through thecolloid mill until homogenation of the oil in water is achieved.

EXAMPLE VII (AEROSOL FORMULATIONS) Into a cylinder rated at 100 p.s.i.working pressure, is.

introduced 10 parts of Compound VII. The cylinder is then made pressuretight except for one opening through which is introduced a mixture of 10parts acetone and 50 parts of dichloro difluoromethane from a containerat 2000 p.s.i. The cylinder into which the ingredients are introduced isthen sealed off and inverted to give a uniform aerosol solution of myactive materials in the mixture of co-solvents.

EXAMPLE VIII (OINTMENT) 2000 parts of Compound VIII is ground in a ballmill until it is no longer gritty and then passed through a fine meshsieve. mixing vessel and 10,000 parts of white petrolatum, U.S.P.

is added. The mixture is mixed until all powder is sus-.

pended within the petrolatum in the form of a fine paste. Then theremainder of 998,000 parts of white petrolatum is added and the mixtureagain thoroughly mixed until a homogenous product is obtained.

The fungicidal effectiveness of my compounds was. demonstrated by one ormore of the following tests.

Agar-Plate Technique The compounds were screened for anti-fungalactivity by the agar-plate technique against five fungi representin Thepowder is then transferred to a suitable.

groups of economic importance. their occurrences are as follows:

The test fungi and Specifically, the method was the Agar-PlateTechnique, USDA Circular No. 198, pages 12 and 14, 1931. The mediumemployed was Sabouraud Dextrose Agar. This medium is used for carryingthe stock cultures as well as for the test itself. The agar is put intosolution and then cooled to 42-45 C. To this is added a saline sporesuspension of the test organism. The inoculated agar is then poured intosterile Petri dishes and allowed to harden. A suitable amount of thecompound tested was placed on a one square centimeter area in the centerof the agar. If the compound was solid, the compound was sprinkled uponthis area of the plate. When the compound was a liquid, a depression wascut out in the center of the agar by means of a cork borer having adiameter of 1.5 mm. Four drops of the liquid compound were placed inthis depression. The agar plates were incubated for days at C. If thecompound is inhibitory, a zone of clear agar will be noted around thearea of inoculation. The size of this zone is measured, and is anindication of the inhibitory value of the compound tested. Thediffusibility of the compound will affect the area of inhibition. If thecompound tested has no antifungicidal activity, there will be no area ofinhibition, and in some cases, growth will appear under the compoundtested.

Serial dilution tests The sample was tested for activity against thesame five fungi utilized in the Agar Plate Technique. The fungi for alltests were grown in a Bacto Sabouraud Liquid Mediuni, pH of 5.7. Thesample was dissolved in a minimal quantity of ethanol and diluted withsterile water thereatfer to give an original concentration of 512 p.p.m.The test cultures were grown upon the Bacto Sabouraud Dextrose Agar for10 days. A heavy spore suspension Was prepared in buffered distilledwater. The inoculum for each tube was one drop of the heavy sporesuspension. The test cultures were incubated at C. for 10 days. Aneffective concentration of 250 parts per million (p.p.m.) is generallyaccepted as the maximum concentration at which a chemical can beconsidered for use as an agricultural fungicide.

Further screening of representative types of these compounds was carriedout by the serial dilution test according to Burlingame and Reddish, J.Lab. Clin. Med. 24, page 765, 1939. The test fungi used in this casewere T richophyton interdigitale, T richophyton rubrum, T rycophytonschoenlez'nii, Microsporum audo uz'ni, Epidermophyton floccosum,Microsporum gypseum. These fungi were grown in Difcos Sabourauds liquidmedium, pH 4.7. Sample preparation consisted of dissolving aliquots ofeach compound in 10 mls. of ethanol and diluting to 512 ppm.concentrations with distilled Water. These stock solutions were seriallydiluted through 10 tubes of culture medium. The inoculum consisted of 1drop per tube of a heavy spore suspension of the test fungi. The testswere incubated at C. for one week.

Particular effectiveness of the samples in this series of testsindicates possible therapeutic use in the treatment of athletes foot,ringworm of the nails and scalp and external fungal infection ofanimals. Some presently commercial fungicides, utilized in this field oftherapy, contain an active ingredient in concentrations as high as 30percent by weight (300,000 parts per 1,000,000).

8 F oliar fungicide screening Cereal leaf rust wheat.Is grown in soil inpaper pots with 20-30 plants per pot. When the plants are 68 inchestall, they are sprayed With the test solutions, 300 p.p.m. and p.p.m.concentration) with three pots used for each treatment applied. Afterthe spray treatments have dried thoroughly, the plants are sprayed witha suspension of spores of wheat leaf rust disease, Puccinl'a rubigovera,reared on live wheat leaf culture. After one Week to ten days, diseasesymptoms are observed and percent control obtained by comparison of thesample with inoculated controls and manzate-treated positive controls.

Tomato late bliglzt.-Susceptible species tomato plants are treated fromseed and transplanted into soil in individual paper pots. When they are6 to 8 inches high, they are sprayed with the test solutions (300 p.p.m.and 75 p.p.m. concentration) with three plants used for each treatmentapplied. After the spray treatments have dried thoroughly, the plantsare sprayed with a suspension of spores of the tomato late blightfungus, Plzytophthora infestans, which is reared on lima bean agarculture. After a few days to one Week disease symptoms are observed andpercent control obtained by comparison of the sample with inoculatedcontrols and manZate-treated positive controls.

Powdery mildew of cucumbers. Susceptible species cucumbers are grown insoil in paper pots with 2-3 plants per pot. When the first leaf hasreached a size of about 3 inches in diameter, they are sprayed with thetest solutions (300 p.p.m. and 75 p.p.m. concentration) with 3 pots usedfor each treatment applied. After the spray treatments have driedthoroughly, the plants are dusted with spores of powdery mildew fungus,Erysiplze cichoracearum, reared on live cucumber leaf culture. After oneweek to ten days, disease symptoms are observed and percent controlobtained by comparison of the sample with inoculated controls andKarathane-treated positive controls.

Agar Plate Serial Dilution Minimum effective concentration in p.p.m. 250p.p.m. or less considered good activity Zone of inhibition inmillimeters *An Pe As Go Ti An Pe As Ge Ti Mercuric salt ofcyclopentadienyl chromium tricarbonyl 13 22 40 27 3 512 512 512 128 16Cyclopentadienyl molybdenum iodide tricarloonyl 17 40 40 40 40 256 12832 128 64 solani; Gc= Glomerella cingulata; Ti= Trycophytoninterdigz'tale.

Serial dilution FUNGI PATHO GENIG TO MAN AND ANIMALS [Minimum effectiveconcentration in parts per million] *An=AspergilZus nigcr;Pe=PeniciZZium ezpansum; As=Altcr7 zaTia *Ma. Mg Tr Ef Ts Ti Mercuriesalt of cyclopentadienyl chromium tricarbonyl. 512+ 512 512 512 512Cyclopentadienyl molybdenurn iodide tricarbonyl-.. 126 16 8 128 64 (b)from 0.1 to 5 Weight percent of a surface active dispersing agent as adispersant therefor, and

(c) the remainder of said composition consisting essentially of a solidcarrier selected from the class consisting of talc, attaclay,kieselguhr, chalk, diatomaceous earth, soybean flour, tobacco flour,Walnut shell flour, gypsum, mica, apatite, pumice and fullers earth.

2. A fungicidal composition of claim 1 wherein said principal activeingredient is the mercuric salt of cyclopentadienyl chromiumtricarbonyl.

3. Method of combating fungi comprising treating the locus of the fungiwith a fungitoxic amount of a compound selected from the classconsisting of the mercuric salt of cyclopentadienyl chromiumtricarbonyl, the cadmium salt of methylcyclopentadienyl chromiumtricarbonyl, the sodium salt of methylcyclopentadienyl chromiumtricarbonyl, and the copper salt of cyclopentadienyl chromiumtricarbonyl.

4. Method of combating fungi comprising treating the locus of the fungiwith a fungitoxic amount of the mercuric salt of cyclopentadienylchromium tricarbonyl.

References Cited by the Examiner UNITED STATES PATENTS 2,178,099 10/1939Gornitz et al 260431 2,208,253 7/1940 Flenner et al. 167-22 10 2,278,9654/ 1942 Van Peski et a1 260429 2,818,416 12/1957 Brown et al 2604292,818,417 12/1957 Brown et a1 260429 2,839,552 6/1958 Shapiro et al.260429 2,864,843 12/1958 De Witt et al. 260429.9 2,898,354 8/1959Shapiro et al 260429 2,916,503 12/ 1959 Kozikowski 260429 2,964,547 12/1960 De Witt et al. 260429 2,964,548 12/1960 Brown et al. 2604292,976,285 3/1961 Gash 260242 2,976,303 3/1961 Shapiro et al. 2604292,976,304 3/1961 De Witt et a1 260429 2,988,562 6/1961 Weinmayer 2604392,988,564 6/1961 Graham 260439 3,007,953 11/1961 Closson et a1. 2604293,009,766 11/1961 Sandel 23-14 3,030,399 4/1962 Thomas 260438 3,032,5705/1962 Haslam 260429.5 3,035,074 5/1962 Haven 260439 OTHER REFERENCESEncyclopedia of Chemical Technology, entires: Carbonyl Compounds,Carbonyl, vol. 3, pp. 201-205, published 1949 by InterscienceEncyclopedia, Inc., N.Y., N.Y.

LEWIS GOTTS, Primary Examiner.

MORRIS O. WOLK, Examiner.

1. A FUNGICIDAL COMPOSITION CONSISTING OF (A) AS A PRINCIPAL ACTIVEINGREDIENT, FROM 0.001 TO 30 WEIGHT PERCENT OF A COMPOUND SELECTED FROMTHE CLASS CONSISTING OF THE MERCURIC SALT OF CYCLOPENTADIENYL CHROMIUMTRICARBONYL, THE CADMIUM SALT OF METHYLCYCLOPENTADIENYL CHROMIUMTRICARBONYL, THE SODIUM SALT OF METHYLCYCLOPENTADIENYL CHROMIUMTRICARBONYL, AND THE COPPER SALT OF CYCLOPENTADIENYL CHROMIUMTRICARBONYL, (B) FROM 0.1 TO 5 WEIGHT PERCENT OF A SURFACE ACTIVEDISPERSING AGENT AS A DISPERSANT THEREFORM, AND (C) THE REMAINDER OFSAID COMPOSITION CONSISTING ESSENTIALLY OF A SOLID CARRIER SELECTED FROMTHE CLASS CONSISTING OF TALC, ATTACLAY, KIESELGUHR, CHALK, DIATOMACEOUSEARTH, SOYBEAN FLOUR, TOBACCO FLOUR, WALNUT SHELL FLOUR, GYPSUM, MICA,APATITE, PUMICE AND FULLER''S EARTH.